Preparation of methyl chloride and methylene chloride



No Drawing. Application n e member 2a, l9 27 s erial no. 345,20 an d' in cermg ma "18,: 1 92711 Patented-[July 18, c v

WALTER VBERNDT Ami om nnnsnfor HocHs'r-oN-rHn-MMN ennmani-nssrenons (:PERIVIANY, A CORPOLBATIONzOF GERMANY TO I. G. FARIBENINDUSTRIE AKTIENGESELLSCHAIT, or FRANKFonrgoN-rmammm .v

PREPARATION or mngrniyfri eiinonlnn nn mmfnym amm f Our present invention relates to a new' process of preparing halogenated organic compounds.

" When exchanging in organic compounds hydrogen for halogen, hydrogenhalide is obtained as ,a by-product. In many cases it is desirable to remove it by achemical formation in a useful manner.

Now we have foundthat'thei hydrogen substitution product, a quantityj ofan alihalide can easily befreinolved by directlyiadd ucts an'alcohol, particularlymethanol, and

causmg it to react with the: hydrogen halide, with or Without the application of a catalystorfpressure; so as to obtain the correspoi d ing alkylhalide and water. Thus, by combiningthe halogenation and the treatment of the hydrogen halide "thereby formed with an alcohol there is obtained at the final stage i I of theprocess besides some water a mixture.

of'the halogenated startingmaterial with an alkyl jhali-de which can beseparated or??? reaction products can be easilyseparated therefrom. In this particular case the methyl chloride thus obtained can immediately be subjected to the reaction with. chlorine in the cycle of the process. When applying the said process tothe chlorination of methane, the amount ofth'e methane chlorides can be increased by the quantity of methyl chloride corresponding to the quantity of hydrogen chloride tained in the chlorination products.

In other cases, forinstance in the chlori nation ofbenzene there isobtained a mixture of the high-boiline chlorosubstituted starting material with the "lowfboiling alkyl chloride, which mixture can easily be sop In every case the value of our present in vention resldes 1n the d rect transformat on of the disagreeable hydrogen halide rem-ea transingto the mixture of the halogenationprodthrough a (11:0 3550 directly to the mixture of the halogenation" product'scontaining besides more or less un-j 1, altered starting ll'lfitBIlflLtlifl halogen-sub I stltution product which has formed and a quantity of-hydrog en halideequivalentftothe' phat-i0 alcohol being equal nolecularly to-that i I of the hydrogen halide' presentL Thefimix turethus obtained can becaused toreact'in a knowninanner, so thatthe reaction of the alcohol withthe hydrogen halide leading-F to the formation of the corresponding alk ylhalideand Water take'splaceaccording to the ,fol'lowing equation 1 F T wherein R- standsjfor anlaliphati c residue; f and Xfor a halogen. The'con'ditions oftlie reaction vary according to the process apa plied, Thereaction canj occur in a generally. I known manner, for-instance in the presence of .boiling,' aqueous halogen hydracid l at a' tenip'eratu 'eof about 10090. or in the-gaseous phase over suitable Contact substances,in' pare;

stances, "attemperatures -varying between 150 C. and 350 Qor 'under'pressur'ein. the

vpresence or absenceiof water and a catalyst.

Theiss'eparation of "tlie miizture so'obtained is like-wise. efl'ected in-known manner by 'fra'ctional condensatiom distillation,"adsorption or the like, I

The following ,xmhple's inertia-0a in vention, but they are not intendedto limit,

(31-1 01 'andl vpart by volume of C1 is conducted at her to re acti onwith boiling methanol the-rate of 120 liters per .hour f reaction chamber 'heated-ot'3 60 1 C. having'a' capacity of'750'lto 800 com: The chlorination product leaving the.

themethanol and hydrochloric acid are the water is drawn off pari passu with itsformatlon, a-gaseous mixture of about 3 parts transformed into CH Cl and HO. While by volume of (H 01 and 1 part-by olume'of GH Cllleaves' the reaction chamber. After the separation has been effected, the 3 parts by volume of (II-I 01 after being mixed with 1 partby Volume of C15 are reintroduced into the chlorination process. The said chlorination. product subjected to the reaction with gaseous methanol' according to the indications of Example 2. v 4

A mixture of 10 parts by volume of methane and 1 part by volume-of chlorine is pressed througha tube heated to 370. C;

I The reaction mixture consists of-about 9 parts "byvol'ume of methane, '1 part by volume of 2 0 methyl chloride togethenwith small quantities of higher-chlorinated -products and 1 l party-by volumeof hydrogen chloride; To

this I mixture is added gaseous. methanolin a quantity corresponding to the quantity of" hydrogen chloride contained in the mixture allCltl'le Whole isvpassed directly through a second reaction tube containing a; catalyst heated to about .160? Co. to 200 C for in stance silica-gel loaded with Zinc I chloride. In this tube the transformation of CH OH+HCl to GH Cl-l-H O is effected. Thevgas mixture leaving the tube now consists of about 9 parts by volume of methane, 2

parts by volume of methyl chloride together 7 with slight quantities of higher-chlorinated productsand l partby olumeof water vapor,

300 pa rts by Weight of benzoli 1 part by w'eight of iron and 1 part by weight of ironchloride are placed intoaclosed vessel fandinto this mixture are ;first gradually pressed 156 parts by weightof-chlorine.

a After the chlorinehasbeenconsumed 110 parts by weight ofalcohol of '92 per cent.

strength vare introduced into the autoclave chlorobenzene and small quantities 619 1.24?

underpressure and the whole is then heated to C5; for 3 hours. When the reaction is complete the content of the autoclaveis frac- I tionated; In this manner there are'obtained parts by Weight of ethyl chloride 2l3 parts by. weight of chlorobenzene, besides unconsumedxbenzol, some orthoand para-ditrichlorobenzene, aqueous hydrochloric acid andunconsumed alcohol. i

I 'Inthe following claims the expression a to agents capable of promoting the reaction is to 'be', understood to comprise theuse of ,a

icatalyst or' pressures.

We claim:

' 1. The processwhich .comprises'causing v'aporous methanol to act upon the reaction product obtained by the halogenation of methyl chloridetand containing the hydrogen may also be- 'halogenation,i1'1 the presence of a catalyst the formula 1.

halide which has been liberated during'the 1 halogenation in the presence of a catalyst heated to C. to 350C. selected from the group of the catalysts known to promote the reaction between hydrochloric acid and methanol to form methyl-chloride and water.

2. The process which comprises causing vaporous methanol to act upon the 'reactlon product obtained by i thehalogenation of methyl chloride and containingthe hydrogen halide which has been liberated during the heated to C. to 200 0. comprising a carrier charged with zinc chloride.

p 3; The process which comprises passing over a catalyst heated to about 160 C. to

with the gaseous reaction product obtainable by'condu'cting. a mixture of 3 parts by V0 l- 200-? C1 and comprising a: carrier loaded with zinc chloride, vaporousm'ethanol together uane of methyl chloride and 1 part Volume of chlorine'through a reaction chamber heatedto 360C. 130,380? (3., which reaction product contains the 'gaseous;1 hydrochloric acid liberatedduringthe process, the quantity of thevaporous methanol beinq-equal-imolecdrochloric acid.

ularly to that of gaseous y present y I t The process which comprises causing methanol to act upon the reaction mixture'obtamed by the chlor natlon of. acompound of e wherein X represents hydrogen or chlorine so as to}transfo'rm the hydrogen chloride con; tained ,th'erein'into' m ethylchloride.

'. v5; Theprocesswhich comprises acting, in

wherein represents hydrogen or chlorine,

- so asto transform the hydrogen chloride contained therein intomethylchloride.

'6.1 The process which comprisesacting in v the presenceof a metal halide known to pro drogen chloride to form methylchloride and ture obtained by the chlorination of a compound of the formula wherein X represents hydrogen orchlor'ine,

, w a #12 mote the reactlon between methanol and hy- Water, with methanol upon the reaction mix;

.so as to transformthe hydrogen chloride contained therein into methylchloride;

7. The process Which comprises acting,in

the presence of highly-porous substances 1. y

tained by the chlorination of'methylchloride',

knownto promote the reactionbetween inethanol and hydrogen chloride; to form methyl- 1 tamed-therein into inethylchloride,"and reintroducing the methylchloride thus formed into the chlorination process;

chloride and water, with inethanolupon the vreaction mixture obtained bythechlorina 9 tion of a compound of the formula a n-o-x H Y I wherein X represents hydrogen or chlorine, so as to transform the hydrogen chloride contained therein into methylchloride.

8. The process which'comprises acting, in

the presence of a carrier charged with zinc chloride, upon the reaction mixture obtained bythe chlorination of a compound of theformula 1 i i a a H .H C-X 11 wherein X" represents hydrogen chlorine, so as to transform the hydrogen chloride contained therein into niethylchloride.

9. The process which comprises ca-using" vaporous methanol to act uponthe reaction mixture obtained by the chlorination of a compound of the formula IH OX f, y

so as to transform the hydrogen chloride contained therein into methylchloride.

10. The process which comprises acting,-in the presence of an agentv knownto promote the reaction between methanol and hydrogen chloride to form methylchloride and water, with vaporous methanoljupon the reaction mixture obtained by the chlorination of a compound of the'formula rQc-x a wherein X represents hydrogen or chlorine, I

' so as to transform the hydrogenchloride contained therein into methylchloride.

11;Theprocess which comprises acting with methanol upon the reactionnmixture; obtained by the chlorination o'f methychlo with methanol upon the reaction mixture 010- so as to transform thehydrogen chloride con 13. The process which comprises acting,;iii

14; The process zwhi h .c'omprisesacting1 drogen chlori e ride, so as totraiisform the hydrogen chlocl a a ride contained therein into methylchloride. 12.The process which comprises acting" thelpresence ofansagent knownto promote a y the reaction between'methanol and hydrogen chloride toform methylchloride and Water, with methanol upon the reaction mixture ob ta-ined the chlorination of methylchloride,.

so ast'o transform the hydrogen chloride con} ",tained the-rein into methylchloride and rer i. V introducing the methylchloride thus formed into the chlorination process.

I with vaporous methanol upon the reaction:

mixture obtained lbyl the-chlorination of methylchloride, so as to; transfor 'in the hycontained; therein" into l in the presence o'f' an agentlknown topro-u,

drogen] chloride to form methylchlorideand water, with Vaporous methanol upon there action mixture obtained by the chlorination therein into methylchlorideg 17. The process wh'ch', comprises actii gl mote the reactionbetween methanol and hyof methylchloride, soas, to transform the hydrogen chloride contained I therein into methylchlor'ide. U603 L with methanol upon the reaction mixture obi i to transform the hydrogen chloridecontained Q I withw'aporous, methanol "upon jthe're'action mixtureobtained by the chlorination of neth ane, so as to transform thehydrogen chloride contained therein'into methylcliloride; c a 18. The process which comprises acting in the presence of an agent known-to promote a y the reactionbetween methanol, and hydrogen} chlorideto form methylchloride and {water .with vaporouslmethanol;upon the reaction mixture obtained by the'chlorination of methanel, so as to transform the hydrogen-chloride contained therein into methylchloride. a WALTER BERNDT. 1

.O TQ R 

